CN105602102A - Low-density, high-strength and scratch-resistant modified polypropylene composite material and preparation method thereof - Google Patents
Low-density, high-strength and scratch-resistant modified polypropylene composite material and preparation method thereof Download PDFInfo
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- CN105602102A CN105602102A CN201511020392.9A CN201511020392A CN105602102A CN 105602102 A CN105602102 A CN 105602102A CN 201511020392 A CN201511020392 A CN 201511020392A CN 105602102 A CN105602102 A CN 105602102A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Abstract
The invention discloses a low-density, high-strength and scratch-resistant modified polypropylene composite material and a preparation method thereof. The polypropylene composite material is prepared from the following components by weight percent: 46-89% of polypropylene, 5-15% of toughening agent, 5-20% of inorganic filler, 1-10% of glass beads, 0-3% of coupling reagent, 0.1-2% of antioxidant, 0.1-1% of light stabilizer and 0-3% of others. The polypropylene composite material not only has excellent scratch resistance and higher tensile strength, but also has lower density, thus better meeting the requirements of scratch resistance and light weight of the automobile industry for interiors and exteriors of automobiles.
Description
Technical field
The present invention relates to a kind of low-density, high strength, scratch-resistant modified polypropylene composite material, of the present invention poly-Acrylic composite has the advantages such as technique is simple, scratch-resistant, can realize the lightweight of vehicle material simultaneously.
Background technology
Along with the fast development of automobile industry, security, comfortableness, lightweight, low smell etc. become automobile workThe main trend of industry development. Polypropylene has that processing characteristics is good, cost performance is high, heat-resisting and chemical drugs moral character is goodEtc. advantage, be widely used in inner and outer decorative parts of automobile, as instrument board, door-plate, column, bumper etc.
Current people, along with the continuous change of consumption idea, also carry aesthetic property, the feature of environmental protection etc. of automotive upholsteryGo out higher requirement. Especially scraping and wiping resistance performance largely affects the aesthetics of product compared with missionary society, simultaneously vapourCar parts, in transport assembling or use procedure, can inevitably produce cut, slight impact etc., and this willCause product to occur blushing, affect the presentation quality of product.
Patent CN101173074A discloses a kind of polypropene composition and preparation thereof with scratch resistant performanceMethod, this has in the polypropene composition of scratch resistant performance and adds erucyl amide auxiliary agent, for improving polypropyleneThe surface property of composite, reduces the coefficient of friction of material, thereby improves scratch resistant performance. But, due toThe smell of erucyl amide is larger, affects the distribution performance of product; Patent CN101864115A discloses a kind of resistance toThe shock proof propylene-ethylene block copolymerization polypropylene modified material of swiping, it has selected a kind of special propylene-secondAlkene block copolymerization polypropylene improves the scraping and wiping resistance performance of polypropylene material. But the intensity of material is significantly fallenLow, thus cannot meet actual instructions for use; Patent US7208536 discloses a kind of scratch-resistant polypropyleneComposite, it is by add rubber components in high-crystallinity polypropylene, inorganic filler and aluminium base siloxanes look motherGrain is made scratch-resistant polypropylene, and the surface tension of this kind of high polysiloxanes is less, in forming process, can moveThe thin layer that forms a lubricant molecule to product surface, this kind of surface lubrication can reduce surface tear and rubThereby wipe the surperficial scratch resistant performance of coefficient raising material. But, because the price of organosiloxane is higher, largeIncrease greatly the cost of material.
Summary of the invention
The object of the invention is to develop the simple PP composite material of a kind of technique, this composite has wellScraping and wiping resistance performance and hot strength, density is lower simultaneously, can meet the light-weighted requirement of auto parts and components.
The object of the invention is to be achieved through the following technical solutions:
A kind of low-density, high strength, scratch-resistant modified polypropylene composite material, comprise following by weightRaw material:
Described polypropylene melt flow rate (MFR) under 230 DEG C, 2.16kg loading condiction is 2～60g/10min.
Described polypropylene is homo-polypropylene or block copolymerization propylene; The degree of crystallinity of homo-polypropylene is 70～100%,Isotacticity is 99～100%; The comonomer of block copolymerization propylene is ethene, vinyl monomer repetitive moleContent is 4～10%.
Described flexibilizer is ethylene-octene linear copolymer, and preferred density is 0.88～0.90g/cm3,The linear copolymerization of ethylene-octene that under 230 DEG C and 2.16kg loading condiction, melt index is 0.5～10g/10minThing.
Described inorganic filler is one or more combination thing in talcum powder, calcium carbonate and wollastonite.
The density of described glass microballoon is 0.25-0.5g/cm3, particle diameter is 30～100 microns.
Described coupling agent is the one in silane coupler, titanate coupling agent and aluminate coupling agent.
Described antioxidant comprises primary antioxidant and auxiliary anti-oxidant; Primary antioxidant is in hindered phenol and sulphur ester antioxidantOne or more mixing; Auxiliary anti-oxidant is one or more mixing in phosphite and ester kind antioxidant.
Described light stabilizer is hindered amine light stabilizer.
Described other auxiliary agent comprises shades of colour additive, various ester class or fatty acid lubricant etc.
Above-mentioned low-density, high strength, scratch-resistant modified polypropylene composite material, preparation method's step is as follows:
(1) take each component by above-mentioned weight proportion;
(2) polypropylene, flexibilizer, inorganic filler, glass microballoon, coupling agent, antioxidant, light are stablizedAgent and other auxiliary agent are dry mixed 3～5 minutes in super mixer;
(3) step (2) products therefrom is placed in to dual-screw-stem machine, through melt extruding, granulation, its techniqueFor: 200～210 DEG C, a district, two 210～220 DEG C, districts, three 210～220 DEG C, districts, four 205～215 DEG C, districts;The time of staying is 1～2 minute, and pressure is 12～18Mpa.
The invention has the advantages that:
1: the prepared modified polypropylene composite material of the present invention has excellent scraping and wiping resistance performance and higher drawingStretch intensity.
2: the prepared modified polypropylene composite material density of the present invention is lower, can meet auto parts and components lightThe requirement quantizing.
3: preparation method's technique of the present invention is simple, and cost is lower.
Detailed description of the invention
In low-density of the present invention, high strength, scratch-resistant modified polypropylene composite material, comprise that quality percentage containsAmount is that 46～89% melt flow rate (MFR) (test condition: 230 DEG C, 2.16kg load) is 2～60g/10minHomo-polypropylene or block copolymerization propylene (comonomer of block copolymerization propylene is that its content of ethene existsIn the scope of 4～10mol%; The degree of crystallinity of homo-polypropylene is more than 70%, and isotacticity is greater than 99%); QualityPercentage composition is 5～15%, density is 0.88～0.90g/cm3, melt index be 0.5～10g/10min (surveyExamination condition: 230 DEG C, 2.16kg load) ethylene-octene linear copolymer as flexibilizer; Quality percentageThe talcum powder of content 5～20%, calcium carbonate, wollastonite a kind of or their composition etc. are as inorganic filler;Quality percentage composition is 1～10%, and density is 0.25-0.5g/cm3, particle diameter is that the glass of 30～100 microns is micro-Pearl; Quality percentage composition is one in 0～3% silane coupler, titanate coupling agent or aluminate coupling agentPlant coupling agent. Also comprise with the primary antioxidant of one or more compositions in hindered phenol or sulphur ester antioxidant and withThe auxiliary anti-oxidant of one or more compositions in phosphorite kind antioxidant is the antioxidant of component, this antioxygenThe mass percentage content of agent in polypropene composition of the present invention is 0.1～2%. Also comprise quality percentage compositionIt is 0.1～1% hindered amine light stabilizer. Can also comprise that quality percentage composition is other auxiliary agent of 0～3%Comprise shades of colour additive, various ester class or fatty acid lubricant etc.
Before use, take raw material by said components and weight proportion, in super mixer, be dry mixed 3～5 minutes;The raw material of mixing is placed in to dual-screw-stem machine, and through melt extruding, granulation, its technique is: 200～210 DEG C, a district,Two 210～220 DEG C, districts, three 210～220 DEG C, districts, four 205～215 DEG C, districts; The time of staying is 1～2 minute,Pressure is 12～18Mpa.
Mode below by embodiment further illustrates the present invention, described in therefore not limiting the present invention toAmong scope of embodiments.
Embodiment 1
PP composite material key component of the present invention comprises 81.3% polypropylene, 5% flexibilizer, 7% talcumPowder, 3% glass microballoon, 1% coupling agent, 0.1% antioxidant 3114 and 0.2% irgasfos 168,0.2% lightStabilizing agent 944 and 0.2% light stabilizer 770 and 2% other auxiliary agent.
Embodiment 2
PP composite material key component of the present invention comprises 76.3% polypropylene, 5% flexibilizer, 10% talcumPowder, 5% glass microballoon, 1% coupling agent, 0.1% antioxidant 3114 and 0.2% irgasfos 168,0.2% lightStabilizing agent 944 and 0.2% light stabilizer 770 and 2% other auxiliary agent.
Embodiment 3
PP composite material key component of the present invention comprises 69.3% polypropylene, 8% flexibilizer, 12% talcumPowder, 7% glass microballoon, 1% coupling agent, 0.1% antioxidant 3114 and 0.2% irgasfos 168,0.2% lightStabilizing agent 944 and 0.2% light stabilizer 770 and 2% other auxiliary agent.
Embodiment 4
PP composite material key component of the present invention comprises 63.3% polypropylene, 8% flexibilizer, 15% talcumPowder, 10% glass microballoon, 1% coupling agent, 0.1% antioxidant 3114 and 0.2% irgasfos 168,0.2%Light stabilizer 944 and 0.2% light stabilizer 770 and 2% other auxiliary agent.
Above-described embodiment main component quality percentage composition is in table 1.
Table 1 embodiment 1～4 key component content (quality percentage composition)
Comparative example 1
This comparative example PP composite material key component comprises 81.3% polypropylene, 5% flexibilizer, 10% cunningStone flour, 1% coupling agent, 0.1% antioxidant 3114 and 0.2% irgasfos 168,0.2% light stabilizer 944With 0.2% light stabilizer 770 and 2% other auxiliary agent.
Comparative example 2
This comparative example PP composite material key component comprises 76.3% polypropylene, 5% flexibilizer, 15% cunningStone flour, 1% coupling agent, 0.1% antioxidant 3114 and 0.2% irgasfos 168,0.2% light stabilizer 944With 0.2% light stabilizer 770 and 2% other auxiliary agent.
Comparative example 3
This comparative example PP composite material key component comprises 69.3% polypropylene, 8% flexibilizer, 19% cunningStone flour, 1% coupling agent, 0.1% antioxidant 3114 and 0.2% irgasfos 168,0.2% light stabilizer 944With 0.2% light stabilizer 770 and 2% other auxiliary agent.
Comparative example 4
This comparative example PP composite material key component comprises 63.3% polypropylene, 8% flexibilizer, 25% cunningStone flour, 1% coupling agent, 0.1% antioxidant 3114 and 0.2% irgasfos 168,0.2% light stabilizer 944With 0.2% light stabilizer 770 and 2% other auxiliary agent.
In comparative example, carry out instead of glass microballon with talcum powder, other key components are consistent with embodiment, each mainConstituent mass percentage composition is in table 2.
Table 2 comparative example 1～4 key component content (quality percentage composition)
In above-described embodiment and comparative example composite-material formula, described polypropylene is co-polypropylene, melt-flowMoving speed is 30g/10min. Described flexibilizer POE is linear ethylene-Xin that Dupont company of the U.S. producesAlkene copolymer, trade names are Engage8180, density is 0.863g/cm3, melt flow rate (MFR) is0.5g/10min. Described inorganic filler is 1250 order talcum powder, and average grain diameter is 10 microns. DescribedGlass microballoon, real density is 0.46g/cm3, average grain diameter is 55 microns. Described coupling agent is the U.S.The silane coupler that DowCorning company produces, trade names are Z-6011. Described primary antioxidant 3114For BASF AG produces, trade names are Irganox3114, and chemical name is 3,5-di-t-butyl-4-hydroxylBase benzyl diethyl phosphate; Auxiliary anti-oxidant 168 is BASF AG's production, and trade names are Irgafos168,Chemical name is three (2,4-di-tert-butyl-phenyl) phosphite ester. Described light stabilizer 944 is BASF public affairsDepartment produces, chemical name for poly-[6-[(1,1,3,3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-is two[(2,2,6,6 ,-tetramethyl-4-piperidyl) imino group]-1,6-oneself two support [(2,2,6,6-tetramethyl-4-piperidyl) imidoBase] }, light stabilizer 770 is produced for BASF AG, and chemical name be pair (2,2,6,6-tetramethyl-piperidyl)Sebacate.
In above-described embodiment and comparative example, each resin and various additive are dry mixed 3～5 points in super mixerClock, then in double screw extruder through melt extruding, granulation, its technique is: 190～200 DEG C, a district, two200～210 DEG C, district, three 210～220 DEG C, districts, four 205～215 DEG C, districts; The time of staying is 1～2 minute, pressesPower is 12～18Mpa.
The particulate material that completes as stated above granulation is dry 2～3 little in the convection oven of 90～100 DEG CTime, and then dried particulate material is carried out on injection (mo(u)lding) machine to injection moulding sample preparation, carry out performance surveyExamination.
Density measurement is undertaken by ISO1183, and specimen size is 10 × 10 × 4mm; Melt index test is pressedISO1133 carries out, and test condition is 230 DEG C × 2.16Kg; Tensile property test is undertaken by ISO527-2, examinationSample is of a size of 170 × 10 × 4mm, and draw speed is 50mm/min; Bending property test is undertaken by ISO178,Specimen size is 80 × 10 × 4mm, and rate of bending is 2mm/min, and span is 64mm; The punching of simply supported beam breachHit intensity is undertaken by ISO179/1eA, and specimen size is 80 × 10 × 4mm, and notch depth is sample thickness three/ mono-, probe temperature is 23 DEG C; The scraping and wiping resistance performance of material is undertaken by the PV3952 of VolkswagenTest, instrument is that Erichsen430P-1 draws lattice instrument automatically, specimen size 50*50*3.2mm, test sample existsBefore test, need place 48 hours at 23 DEG C. Measure and draw lattice region and the not variation of partition territory aberration L with color difference meterΔ L, Δ L is less, and the scraping and wiping resistance performance of illustrative material is better
The mobile performance of material is passed judgment on by melt index, and the combination property of material is close by test gainedDegree, hot strength, bending modulus, notched Izod impact strength etc. are passed judgment on. The embodiment of the present invention 1～4 and rightRatio 1～4 Properties of Polypropylene Composite testing result is respectively in table 3.
Table 3 embodiment 1～4 and comparative example 1～4 Properties of Polypropylene Composite test result
Can find out with the test result contrast of comparative example 1～4 from embodiment 1～4, the interpolation of glass microballoon is rightThe scraping and wiping resistance performance of PP composite material has greatly improved, and hot strength also has obvious raising, simultaneouslyThe reduction of density plays a positive role to the lightweight of material.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention alsoBe not restricted to specific embodiment described above. To those skilled in the art, any the present invention is carried outEquivalent modifications and substitute also all among category of the present invention. Therefore, do not departing from spirit of the present invention and modelEnclose lower done equalization conversion and amendment, all should contain within the scope of the invention.
Claims (10)
1. low-density, high strength, a scratch-resistant modified polypropylene composite material, is characterized in that: compriseBelow raw material by weight:
2. a kind of low-density according to claim 1, high strength, scratch-resistant modified polypropylene composite woodMaterial, is characterized in that: described polypropylene melt flow rate (MFR) under 230 DEG C, 2.16kg loading condiction is2～60g/10min。
3. a kind of low-density according to claim 1, high strength, scratch-resistant modified polypropylene composite woodMaterial, is characterized in that: described polypropylene is homo-polypropylene or block copolymerization propylene; The degree of crystallinity of homo-polypropylene is70～100%, isotacticity is 99～100%; The comonomer of block copolymerization propylene is ethene, vinyl monomer weightMultiple unit molar content is 4～10%.
4. a kind of low-density according to claim 1, high strength, scratch-resistant modified polypropylene composite woodMaterial, is characterized in that: described flexibilizer is ethylene-octene linear copolymer, density is 0.88～0.90g/cm3、Under 230 DEG C and 2.16kg loading condiction, melt index is 0.5～10g/10min.
5. a kind of low-density according to claim 1, high strength, scratch-resistant modified polypropylene composite woodMaterial, is characterized in that: described inorganic filler is one or more combination thing in talcum powder, calcium carbonate and wollastonite.
6. a kind of low-density according to claim 1, high strength, scratch-resistant modified polypropylene composite woodMaterial, is characterized in that: the density of described glass microballoon is 0.25-0.5g/cm3, particle diameter is 30～100 microns.
7. a kind of low-density according to claim 1, high strength, scratch-resistant modified polypropylene composite woodMaterial, is characterized in that: described coupling agent is in silane coupler, titanate coupling agent and aluminate coupling agentA kind of.
8. a kind of low-density according to claim 1, high strength, scratch-resistant modified polypropylene composite woodMaterial, is characterized in that: described antioxidant comprises primary antioxidant and auxiliary anti-oxidant; Primary antioxidant is hindered phenol and sulphurOne or more mixing in ester kind antioxidant; Auxiliary anti-oxidant be a kind of in phosphite and ester kind antioxidant orSeveral mixing.
9. a kind of low-density according to claim 1, high strength, scratch-resistant modified polypropylene composite woodMaterial, is characterized in that: described light stabilizer is hindered amine light stabilizer.
10. one of any described low-density, high strength, scratch-resistant modified polypropylene composite wood of claim 1-9The preparation method of material, is characterized in that, its step is as follows:
(1) take each component by above-mentioned weight proportion;
(2) polypropylene, flexibilizer, inorganic filler, glass microballoon, coupling agent, antioxidant, light are stablizedAgent and other auxiliary agent are dry mixed 3～5 minutes in super mixer;
(3) step (2) products therefrom is placed in to dual-screw-stem machine, through melt extruding, granulation, its techniqueFor: 200～210 DEG C, a district, two 210～220 DEG C, districts, three 210～220 DEG C, districts, four 205～215 DEG C, districts;The time of staying is 1～2 minute, and pressure is 12～18Mpa.
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Cited By (7)
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| CN105951203A (en) * | 2016-06-27 | 2016-09-21 | 马海燕 | Anti-aging polypropylene monofilament and production method thereof |
| CN108503953A (en) * | 2018-04-25 | 2018-09-07 | 横店集团得邦工程塑料有限公司 | A kind of modified high crystalline PP composite material and preparation method thereof |
| CN109735007A (en) * | 2018-12-27 | 2019-05-10 | 重庆普利特新材料有限公司 | Light-weighted resistance to scratching, resistance to compression trace PP composite material and preparation method thereof can be achieved in one kind |
| CN109897208A (en) * | 2019-03-28 | 2019-06-18 | 杭州人通管业有限公司 | A kind of fire-retardant corrosion proof cable protection pipe of drag reduction formula and its preparation process |
| CN111925587A (en) * | 2020-08-21 | 2020-11-13 | 柳州市海达新型材料科技有限公司 | Modified polypropylene material for hollow building template and preparation method thereof |
| CN113165333A (en) * | 2018-12-14 | 2021-07-23 | 陶氏环球技术有限责任公司 | Multilayer films and laminates containing slip agents |
| CN113563667A (en) * | 2021-07-28 | 2021-10-29 | 重庆普利特新材料有限公司 | Light-weight modified polypropylene composite material for compound filled bumper and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105951203A (en) * | 2016-06-27 | 2016-09-21 | 马海燕 | Anti-aging polypropylene monofilament and production method thereof |
| CN108503953A (en) * | 2018-04-25 | 2018-09-07 | 横店集团得邦工程塑料有限公司 | A kind of modified high crystalline PP composite material and preparation method thereof |
| CN113165333A (en) * | 2018-12-14 | 2021-07-23 | 陶氏环球技术有限责任公司 | Multilayer films and laminates containing slip agents |
| CN109735007A (en) * | 2018-12-27 | 2019-05-10 | 重庆普利特新材料有限公司 | Light-weighted resistance to scratching, resistance to compression trace PP composite material and preparation method thereof can be achieved in one kind |
| CN109897208A (en) * | 2019-03-28 | 2019-06-18 | 杭州人通管业有限公司 | A kind of fire-retardant corrosion proof cable protection pipe of drag reduction formula and its preparation process |
| CN111925587A (en) * | 2020-08-21 | 2020-11-13 | 柳州市海达新型材料科技有限公司 | Modified polypropylene material for hollow building template and preparation method thereof |
| CN113563667A (en) * | 2021-07-28 | 2021-10-29 | 重庆普利特新材料有限公司 | Light-weight modified polypropylene composite material for compound filled bumper and preparation method thereof |
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